Catalyst for purifying exhaust gas by removing nitrogen oxides and a process for the manufacture thereof

ABSTRACT

Catalyst for purifying exhaust gas by removing nitrogen oxides, which is constituted by forming a diffused layer of copper on the surface of a metallic material of specified shape selected from a group of iron, iron alloys, nickel and nickel alloys; and its manufacturing process.

United States Patent 11 1 Bunda et al.

[ 1 Nov. 25, 1975 1 1 CATALYST FOR PURIFYING EXHAUST GAS BY REMOVING NITROGEN OXIDES AND A PROCESS FOR THE MANUFACTURE THEREOF [731 Assignee: Toyota Jidosha Kogyo Kabushiki Kaisha. Japan 122] Filed: Apr. 2, 1973 [21] Appl. No: 347.042

[30] Foreign Application Priority Data Apr. 1. 1972 Japan 4732864 [52] U.S. Cl -1252/ 455 R; 252/466 J; 252/474;

[51] Int. C13. 801.] 29/14; B011 21/04; B011 23/74 {58] Field of Search 252/474, 455 R, 466 J. 423/2132 213.5

[56] References Cited UNITED STATES PATENTS 3,410,651 11/1968 Brandenburg et a1. 423/21 312 1565574 2/1971 Kearby et al. 1111111 252/474 X 3 773,894 11/1973 Bernstein et a1 252/474 X Primary ExaminerWi J. Shine Attorney, Agent, or FirmStevens, Davis. Miller 8.: Mosher [57} ABSTRACT Catalyst for purifying exhaust gas by removing nitro gen oxides, which is constituted by forming a diffused layer of copper on the surface of a metallic material of specified shape selected from a group of iron, iron a1- loys nickel and nickel alloys; and its manufacturing process.

13 Claims, 5 Drawing Figures U.S. Patent Nov. 25, 1975 Metallic Mcfieriols Cleaning of mercHic muferiols Copper Diffusion- Penefrufion Treofmenf Cleaning after said Treatment Cofolysr for purifying Nifrogen Oxides from Exhqusf Gus FIG.1

Sheet 1 of 3 US. Patent Nov.25, 1975 Sheet20f3 3,922,234

FIG.2

Coroiysf Bed Temperature 9 .t W w m Huh 0 o C c m w b m w M m A o e I l. O O O O O 8 6 4 2 3; at: o rtaa x02 twnaou ummzrzo B cototcoucou 2O 4O 6O 80 I00 I20 I40 I60 FIG.3

CATALYST FOR PURIFYING EXHAUST GAS BY REMOVING NITROGEN OXIDES AND A PROCESS FOR THE MANUFACTURE THEREOF BACKGROUND OF THE lNVliN'llON:

The conventional industrial catalysts available for purification of auto exhaust gas include precious metal catalysts such as Pt, Pd etc. carried by alumina, oxide catalysts such as oxides mainly composed ofNi, Cu etc. being carried by a carrier or their powder being sinterctli, alloy catalysts mainly composed of Ni, Cu etc; and surface-treated catalysts such as copper-plated stainless steel.

l hcse catalysts, however, have all been found unsat istactory for industrial purposes due to the following serious drawliiacks. [n the case of precious metal catalysts, for instance, the materials Pt, Pd etc. are expert si e and short of supply; besides, the process of making ht. alumina carrier carry these metals is costly.

roblems with the oxide catalysts are such that it is relatively difficult to carry oxides on a. ceramic mate rial; they are remarkably inferior in heat resistance and durability; not only is it hard to sinter oxide powder, but also, the obtained sinterings are so low in strength as likely to be broken by vibration in use, which fact hinders the flow of exhaust gas, resulting in deterioratirui of the catalyst performance.

In the case of alloy catalysts, the problems are such, that the contents of Ni, Cu etc. have to be considerably high and accordingly, the material cost becomes high, also, special caution to be taken in the melting and secondary working tends to elevate the manufacturing costs: the metals Ni, Cu etc. which are to play an important role in catalysis, lack in resistance to oxidation and therefore, they are broken by vibration with progress of their oxidation, resulting in a reduced effect of catalysis.

In the case of surface-treated catalysts, the conven tional surface treatment has been coppcr-plating or immersion in copper bath, but the products thus treated have their topmost layer made of pure copper, which exhibits a very inferior effect of catalysis. This necessitates subsequent activation treatment, which increases the cost; besides, there is no established process for this activation treatment.

Stlh'ilvlARY OF THE IHVENTEUN BRIEF ACCOUNT OF THE ATTACHED DRAWINGS if; 1 shows a flow sheet explaining the manufactuz our process according to the present invention,

FIG. 2 graphically illustrates the relation between the itrilyst bed temperature and the l\l()x purifying rate,

lltj, 3 shows a graphic example of the distribution of concentrations of diffused copper in an SPCi catalyst according to the present invention,

2 FIG. 4 shows a graphic example of the distribution ol concentrations ofdiffused copper in an SUS27 catalyst according to the present invention,

PK]. 5 shows a graphic example ofthc distribution of concentrations ofdiffuscd copper in an SUHM catalyst according to the present invention.

DETAILED DESCRIPTION OF THE lNv'lriNlltllv The present invention aims at attaining an llltlllhllnil catalyst, free from the above-mentioned drawbacks of the conventional catalysts, which can purify cxhr. gas by removing nitrogen oxides ldcnoted herein NOx) therefrom.

With an eye set on the facts that Cu or Ni is a i which excels in the catalytic effect of purifying no and the surface area of a catalyst has direct relation with catalytic reaction, the present inventors, after con stant research, succeeded in perfecting the present 2'3 alyst and a manufacturing process thereof.

The diffused copper catalyst according to the prescm invention is entirely free from the drawbacks of all. conventional catalysts and it can exhibit a superior a i alytic effect in a wide range of temperatures o. 400C.

The following is a more detailed account ofeach hilt in the manufacturing process of the catalyst accoroin to the present invention. The manufacturing prououtlined in the flow sheet of FIG. 1.

Metallic materials Cleaning of metallic materials For the purpose of degreasing and derusting, them: materials are, depending on their surface condition subjected to alkaline treatment of pickling. They do w. tl always need such a cleaning.

Copper diffusion-penetration treatment The following methods are available for copper diffs sion-penetration of the metallic material.

According to one method, the metallic material u buried in a treating composition of copper oxid aluminum powder or magnesium powder and hem 800 l l()OC, thereby causing the following l'tt'lln reaction:

3 CLIO 2m 3 (ii Auo Other methods consist of a gaseous method uielu a halogenized vapor, a powder method utilizing copy powder, and so on.

Any of the above-mentioned methods adopted, but experience shows that the thirdunch tioned method, i.e., the powder method, is the best iui the manufacture of the catalyst according to the pres ent invention.

lin

The application of this powder method is to be described in more detail. All the percentages employed here are in weight percent.

Treating composition Copper powder (4 300 mesh) 95% lnert powder (4 300 mesh) 5 95% Halogen content 0.1

Diffusion-penetration treatment This treatment may be executed in no protective atmosphere, but presence of a protective atmosphere of argon, hydrogen, etc. would assure better results of treatment. For the purpose of treatment, the treating agent and the object to be treated are charged into a vessel and then heated in a protective atmosphere at 600 00C for a specified period. To be able to display a catalytic effect, the formed layer of diffused cop- 4 cold water of both. The catalyst according to the present invention, is produced by these steps.

The following are practical examples of executing the present invention.

EXAMPLE 1 Cold-rolled plate (1.5mm thick), chips produced in cutting rods and wire-net (wire diameter: 0.5 2mm; 4 20 mesh) of five kinds of JlS-specified metals: SPCl,

10 SUS24, SUS27, SUS42 and SUI-I34 were employed.

First, they were degreased in a hot alkaline bath (hot NaOH aqueous solution or hot KOH aqueous solution). Next, they were buried in a treating agent composed of 50% copper powder (I00 150 mesh), 50% alumina powder (100 150 mesh) and 1% ammonium chloride relative to the total weight of Cu and Al; and heated in an argon atmosphere in an electric furnace at 900C for 5 hours of copper diffusion-penetration treatment. Subsequently, they were put to the process of hot water flush cold water flush drying. It is for the purpose of preventing the hardening, when copper powder alone was used, from the same principle as sintering, that the treating agent had been added with alumina powder. Ammonium chloride content in the treating agent had the effect of promoting the penetration of cause there was no difference between the steel plate,

chips and wire-nets.

Table 1 Composition C Si Mn P 5 Cr Ni Materials No.1 SPC 1 0.12 0.25 0.045 0.05

-0.50 No.2 sus24 0.12 0.7s 1.00 0.04 0.03 l6.0

l8.0 No.3 SUS27 0.0a 1.00 2.00 0 04 0.03 18.0 8.0 -20.0 11.0 No.4 SUS42 0.08 1.50 2.00 0.o4 0.03 24.0 19.0 26.0 22.0 No.5 SUH34 0.15 1.50 2.00 0.04 00: 14.0 33.0 l7.0 37.0

per has to fill the following requirements. Considering Table 2 the possibility of an oxidized stripping of the surface Thickness Composition of copper-dilfused layer through repeated cycles of heating and cooling in M fizz? service as the catalyst, the penetrating depth of copper 50 4 1 Cu Fe should be over Sp. at least; and the copper-dlffused No.1 180 5-80 10-90 layer should contain: 20 40 2 5 o s 2 o 90 No.3 90 70-80 s-10 0.5-2 0.5-2 No.4 100 70-90 8-15 0.5-2 0.5-2 9 0 999% No.5 90 -70 lO-20 0.5-2 3-10 NI 0 99.9%

Cu 0.1 95% (necessary by all means) Co andlor Cr up to 40% permissible, since it contributes to the catalytic effect.

Rest less than l 0% Thus, the basic constituent of the copper-diffused layer should be Fe-Cu, Fe-Ni-Cu or Ni-Cu and the other elements should be held below l0%, except Cr and/or Co being less than 40%.

Cleaning subsequent to treatment The major objective of this step lies in washing away the halogens deposited in the copper diffusion-penetration treatment and it is attained by using hot water or mean! mixed presence of Cu and Fe in the copper-diffused layer.

EXAMPLE 2 Same metallic materials as employed in Example 1 atmosphere in an electric furnace at 900C for 5 hours of copper diffusion-penetration treatment. Subsequently, they were washed and dried in the same way as in Example I. The results are summarized in Table 3.

Table 3 Thickness Composition of copper-diffused of copperlayer Materdiffused ials layer (a) Cu Ni Cr Fe No.1 130 5-80 10-90 No.2 110 2-85 0.5-2 10-90 No.3 70 70-80 5-10 05-2 0.5-2 No.4 70 70-90 8-15 -2 0.5-5 No.5 70 50-70 -20 0.5-2 2-10 means the same as in Table 2.

EXAMPLE 3 Using the same metallic materials and the same treating agent as employed in Example 1, 5 hours of copper diffusion-penetration treatment was executed in a hydrogen atmosphere in an electric furnace at 900C, followed by the same washing and drying as carried out in Example 1. The results are summarized in Table 4.

Amount of catalyst:

EXAMPLE 4 thereby determine their catalytic effects.

Apparatus used: NO-removing ability tester using a circulation type mini-reactor (NO-meter employed) Gas supplied comprises- NO 1000 ppm 0 0.24% N: balance 2.75 l/min about 10ml (apparent surface Rate of gas supplied:

area: 100 500cm) Table 4 Spatial velocity: about 16,500 v/ Jhr Thickness Composition of copper-diffused cflmlysl bed temperature-1 about 400C of copperlayer ('36) Materdiffused 1 layer (p) Cu Ni Fe The results are summarized in Table 5.

Table 5 Copper diffusion- Materials penetration treating Activation treating conditions Catalyst form NOx removing rate (76) conditions Example 1 not treated wire-net 43.3 SPC 1 Example 2 not treated wire-net 48.4 Example 3 not treated wire-net 40.5 Example 1 not treated wire-net 38.8 SUS24 Example 2 not treated wire-net 42.2 Example 3 not treated wire-net 413 Sheet 738 not treated Chips 78.2 wire-net 79.5 Sheet 74.2 Example l Oxidized in the atmosphere Chips 85.3 wire-net 81.2 Oxidized in the atmosphere, Sheet 76.3 followed by reduction with Chips 732 hydrogen wire-net 80.3 SUS27 Sheet 81.2 not treated Chips 743 wire-net 83.6 Sheet 78.3 Example 2 Oxidized in the atmosphere Chips 79.6 wire-net 82.4 Oxidized in the atmosphere, Sheet 79.7 followed by reduction with Chips 802 hydrogen wire-net 79.9 Sheet 7 l .2 not treated Chips 733 wire-net 70.2 Sheet 81.3 SUS27 Example 3 Oxidized in the atmosphere Chips 70.4 wire-net 80.9 Oxidized in the atmosphere. Sheet 76.2 followed by reduction with Chips 71.2 hydrogen wire-net 7 1.4 Example 1 not treated wire-net 88.9 SUS42 Example 2 Oxidized in the atmosphere wire-net 81.2 Example 3 Oxidized in the atmosphere. wire-net 85.3

followed by reduction with hydrogen Example 1 not treated wire-net 83.4 Example 2 Oxidized in the atmosphere wire-net 78.1 SUH34 Example 3 Oxidized in the atmosphere. wire-net 85.5 followed by reduction with hydrogen No.1 2-80 10-90 No.2 30 2-85 05-2 10-90 No.3 30 70-80 7-10 05-2 05-5 For the sake of comparison, a surface-treated cata- No.4 30 70-80 7-10 0.5-2 0.5- N05 30 5040 (H 5 o L10 lyst, which represents a copper plated SUS27 sheet,

means the same as in Table 2.

and a similar sheet. activation-treated. were measured for the NOx-removing rate under the same conditions as the above Examples, the results being summarized in 7 Table 6; in each case of surface treatment, the thickness of copper plating was set at 20p.

Table 6 Activation treating conditions NOx removing The above-mentioned catalyst was charged into a catalyst converter, which was then installed 250mm below the exhaust manifold.

rate (71 Non-treated 3.8 Table 8 2 hours oxldized in an atmosphere of 900C l0} 2 hours hydrogen-reduced at 800C 13.2 Engine operation conditions NOx remov- 3 hours diffused in a vacuum at 900C 10.2 ing rate(%) 3 hours diffused in an atmosphere of 900C, followed by 2 hours of oxidation in an 15.4 Eng n tevfllulionl 2,700 '-P- atmosphere of 900C Engine load: 2.2 kg-m 3 hours diffused in an atmosphere of 900C, Spatial velocity; 40,000 v/ /hr followed by 2 hours of hydrogen reduction l4.0 Average gas concentrations. 48.3 at 800C NO: 1,200 ppm. 2 hours oxidized in the atmosphere 900C. C0! 33% followed by 2 hours of hydrogen reduction 68.6 HC: 160 ppm. at 800C C: l2%

Engine revolution: 2,500 r.p.m. Engine load: 1.2 kg-m Further, for comparison, a sheet catalyst of Fe-Cu Spatial velocityi 27900 w Average gas concentrations: 92.4 and Ni-Cu-Fe alloys and a similar catalyst activated, 600 p p m were measured for the NOx removing rate under the CO: 4.6% same conditions as in the above Examples, the results HC: C0,: ll.5% being summarized in Table 7.

Table 7 Alloy composition (95) Catalyst Activation treating NOx remov- No. Cu Ni Fe conditions ing rate a 4.6 balance non-treated 7 .2 b 4.6 Oxidation in hot air 70.3

followed by reduction c 24.0 66.0 non-treated 6.3 d 24.0 66.0 Oxidation in hot air 73.5

followed by reduction e 26.4 52.0 non-treated 5.3 f 26.4 52.0 Oxidation in hot air 78.8

followed by reduction EXAMPLE 5 To determine the relation between the catalyst bed temperature and the NO): removing rate in the catalysts according to the present invention a comparative test under the same conditions as in Example 4 was carrie out except that the catalyst bed temperature was carried out between a wire-net catalyst of SUS27 as obtained in Example 1 and a sheet catalyst No.fof Ni-Cu- Fe alloy. The NO): removing rate of each catalyst was measured with the catalyst bed temperature varied: 300C, 400C, 500C, 600C and 700C, the results being summarized in FIG. 2. According to FIG. 2, in each catalyst compared, a rise in the catalyst bed temperature is accompanied by improvement of the NO): removing rate, but the improvement in the invented catalyst is as great as 97% at 700C.

EXAM PLE 6 Using a wire-net catalyst of SUS27 obtained in Example l, the ability of the invented catalyst to remove the harmful NOx out of emission gases from internal combustion engines was measured and expressed in terms of the following test conditions and the engine operation conditions of Table 8. The results are summarized 60 in the same Table.

(2) Volume of catalyst (3) Catalyst converter EXAMPLE 7 To measure the weight changes due to heating of the invented catalyst in the atmosphere, a sheet catalyst of SUS27 as obtained by the method of Example 1 (50mm d X 35mm, surface area 39.89 cm) was heated at 600C Table 9 NOx revov- Weight loss (mg/cm) ing rate after Heating 100 200 400 400 temperhrs. hrs. hrs. hrs. hrs. of

ature later later later later heatingtk) 600C 6.67 6.75 9.68 [2.60 8L3 700C l L26 14.78 l7.26 l7.06 79.7

The above Examples testify that the invented catalyst makes an excellent means for reducing NOx contained in the emission gases, particularly from internal combustion engines.

A detailed analysis of the results of the above Examples is to be made here. i

As evident from Examples 1 3, the copper-diffused layer of a catalyst according to the present invention using a low carbon steel or a chrome steel as the metallic material represents a mixed layer of Cu and Fe, with Cr practically absent or very little, if present; this is apparent from the distribution of copper concentrations in the diffused layer of the catalyst using SPC l as the metallic material which has been submitted to copper diffusion-penetration treatment, the distribution being illustrated in FIG. 3.

In the case of using nickel steels, e.g., SUS27, SUI- 34 or SUS42 as the metallic material, the copper-diffused layer represents a solid phase of Cu-Ni-(Fe); in this case, the greater the nickel content of the material, the greater become the contents of nickel and iron in the copper-diffused layer with the smaller content of copper. This is apparent from the distribution of copper concentrations in the diffused layer of a catalyst using SUS27 or SUH34 as the metallic material which has been submitted to copper diffusion-penetration treatment, the distributions being illustrated in FIGS. 4 and 5.

From the above, it is easy to infer that through adequate selection of the chemical composition of the metallic material and the conditions of copper diffusionpenetration treatment, copper-diffused layers with a wide range of chemical compositions and thicknesses can be formed on the metallic material.

As seen from Examples 4, 5 and 6 (Tables 5, 7 and FIG. 2), the catalytic effect of a catalyst according to the present invention is equal to or better than that of one using Cu-Ni-(Fe) alloy as the metallic material (which has been submitted to activation treatment) with a corresponding composition of the copper-diffused layer. This is natural in view of the fact that the chemical composition of the copper-diffused layer in the catalyst according to the present invention nearly corresponds to that of the alloy and this is also suggested by the fact that in Table 5, the catalytic effect remains the same in spite of the catalyst being different in form.

As revealed by the comparative test of Example 4 (Tables 5, 6 and 7), surface-treated catalyst and alloy catalyst as received after copper plating, show a very low catalytic effect; they can exhibit a remarkable catalytic effect only after being submitted to activation treatment. By contrast, the catalyst according to the present invention shows a good catalytic effect even without activation treatment and this effect remains practically the same even after such treatment. This fact leads to the speculation that there must be a certain difference other than in the chemical composition between the surfaces of a copper-plated surfacetreated catalyst, a similar catalyst activated; a copperplated alloy catalyst and a catalyst according to the present invention. Cause of this difference cannot be clarified, but it may be surmised that through copper diffusion-penetration treatment, the surface structure of the metallic material in the catalyst according to the present invention is reoriented and activated due to the copper being diffused from outside and penetrating in depth.

As evident from Example 7, according to the present invention, use ofa metallic material which is highly resistant to oxidation makes it possible to obtain a copper-diffused layer that does not strip off even under severe conditions of service, probably because the metal- 10 he material is resistant to oxidation and accordingly, even if the copper-diffused layer becomes oxidized easily, the oxide is not formed in depth under the surface; and the copper-diffused layer is formed in such a network along the crystalline boundary of the metallic material, that it does not strip off easily.

To sum up the advantages of the catalyst according to the present invention, whose excellence as an industrial catalyst for removal of NOx has been described with reference to the above examples:

1. Depending on the metallic material and the conditions of copper diffusion-penetration treatment, the surface composition of the catalyst can be selected over a wide range.

2. The production cost is low, because the copperdiffused layer is formed only on the surface of the metallic material.

3. Through adoption of an anti-oxidizing metallic material the anti-oxidation and anti-stripping properties of the catalyst itself can be improved, resulting in a long persistence of the catalytic effect.

4. The form of the metallic material can be selected over a wide range.

5. Copper-plated surface-treated catalysts and alloy catalysts, when not activation-treated, can hardly be expected to show any catalytic effect; they can be effective only after activation-treated. By contrast, the catalyst according to the present invention shows a catalytic effect just as copper diffusion-treated.

6. The catalytic effect of the catalyst according to the present invention is not affected at all by oxidation or reduction.

These features render the catalyst according to the present invention useful as an exhaust gas'purifying catalyst for internal combustion engines.

What is claimed is:

l. A catalyst for purifying automotive exhaust gas by removing nitrogen oxides therefrom, which is obtained by forming a copper-diffused layer on the surface of a metallic material molded into a desirable shape which is selected from a group of iron, iron alloys, nickel, nickel alloys by burying the molded metallic material in a diffusion-penetration treating agent composed of copper powder, inert powder and halogen compound; and heating this material in a protective atmosphere, whereby a copper-diffused layer is formed on the surface of said metallic material.

2. A catalyst of claim 1, wherein said metallic material is iron or an iron alloy with an iron content of more than 5% by weight.

3. A catalyst of claim 1, wherein said metallic mate rial is nickel or a nickel alloy with a nickel content of more than 0.5% by weight.

4. A catalyst of claim 1, wherein the surface of said metallic material has a copper-diffused layer of at least over 5y. thickness.

5. A catalyst of claim 1, wherein the copper-diffused layer on the surface of the metallic material has been subjected to an activation treatment.

6. A process of manufacturing a catalyst for purifying automotive exhaust gas by removing nitrogen oxides therefrom, comprising the following steps:

molding into a desirable shape a metallic material selected from a group of iron, iron alloys, nickel, nickel alloys;

1 l burying said molded metallic material in a diffusionpenetration treating agent composed of copper powder, inert powder and halogen compound; and heating the above in a protective atmosphere, to form a copper-diffused layer on the surface of said metallic material.

7. A process of manufacturing a catalyst of claim 6, whose metallic material is iron or an iron alloy with an iron content of more than 5% by weight.

8. A process of manufacturing a catalyst of claim 6, whose metallic material is nickel or a nickel alloy with a nickel content of more than 0.5% weight 9. A process of manufacturing a catalyst of claim 6, wherein said inert powder is alumina of kaolin.

ment. 

1. A CATALYST FOR PURIFYING AUTOMOTIVE EXHAUST GAS BY REMOVING NITROGEN OXIDES THEREFROM, WHICH IS ONTAINED BY FORMING A COPPER-DEFFUSED LAYER ON THE SURFACE OF A METALLIC MATERIAL MOLDED INTO A DESIRABLE SHAPE HICH IS SELECTED FROM A GROUP OF IRON, IRON ALLOYS, NICKEL, NICKEL ALLOYS BY BURYING THE MOLDED METALLIC MATERIAL IN A DIFFUSION-PENETRATION TREATING AGENT COMPOSED OF COPPER POWDER, INERT POWDER AND HALOGEN COMPOUND, AND HEATING THIS MATERIAL IN A PROTECTIVE ATMOSPHERE, WHEREBY A COPPER-DIFFUSED LAYER IS FORMED ON THE SURFACE OF SAID METALLIC MATERIAL.
 2. A catalyst of claim 1, wherein said metallic material is iron or an iron alloy with an iron content of more than 5% by weight.
 3. A catalyst of claim 1, wherein said metallic material is nickel or a nickel alloy with a nickel content of more than 0.5% by weight.
 4. A catalyst of claim 1, wherein the surface of said metallic material has a copper-diffused layer of at least over 5 Mu thickness.
 5. A catalyst of claim 1, wherein the copper-diffused layer on the surface of the metallic material has been subjected to an activation treatment.
 6. A process of manufacturing a catalyst for purifying automotive exhaust gas by removing nitrogen oxides therefrom, comprising the following steps: molding into a desirable shape a metallic material selected from a group of iron, iron alloys, nickel, nickel alloys; burying said molded metallic material in a diffusion-penetration treating agent composed of copper powder, inert powder and halogen compound; and heating the above in a protective atmosphere, to form a copper-diffused layer on the surface of said metallic material.
 7. A process of manufacturing a catalyst of claim 6, whose metallic material is iron or an iron alloy with an iron content of more than 5% by weight.
 8. A process of manufacturing a catalyst of claim 6, whose metallic material is nickel or a nickel alloy with a nickel content of more than 0.5% weight.
 9. A process of manufacturing a catalyst of claim 6, wherein said inert powder is alumina of kaolin.
 10. A process of manufacturing a catalyst of claim 6, wherein the halogen compound is furnished by ammonium chloride.
 11. A process of manufacturing a catalyst of claim 6, wherein said protective atmosphere is constituted by argon gas or hydrogen.
 12. A process of manufacturing a catalyst of claim 6, wherein said metallic material buried in the diffusion-penetration treating agent is heated at about 600* - 1100*C.
 13. A process of manufacturing a catalyst of claim 6, wherein said copper-diffused layer is heated in hydrogen gas to subject said catalyst to an activation treatment. 